1486-39-1

The reactions of mixed O,S-esters of tert-butylthiophosphonous acid and dithiophosphorous acid with 1-chloro-2-organylacetylenes were studied.On the basis of them, a convenient method for the synthesis of thioesters of organylethynylthiophosphinic and dithiophosphonic acids, which are undescribed in the literature, was proposed.A difference was found in the chemical behaviour of the methyl ester of S,S-diethyldithiophosphorous acid by comparison with the corresponding complete esters and thioesters of phosphorous acid in reactions with dichloroacetylene.Keywords:thioesters of P(III) acids, 1-chloroacetylenes, organylethynylthiophosphinates, organylethynyldithiophosphonates, Arbuzov reaction.

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The first general and high-yielding synthesis of mixed phosphorotrithioates (R1S)2P(O)SR2 involving white phosphorus, disulfides, and alkyl halides is presented, which provides the shortest and environmentally benign method to synthesize these compounds of practical importance. Only one method for the formation of (R1S)2P(O)SR2 from elemental phosphorus has been developed. Here, with the use of KOH as a base and DMSO-toluene as a solvent, various disulfides couple readily with white phosphorus to give O-potassium S,S-dialkylphosphorotrithioates (R1S)2P(S)OK in almost quantitative yields, which react with alkyl halides to form (R1S)2P(O)SR2 in high yields. The reaction is characterized by the complete conversion of white phosphorus. Moreover, this method can be easily adapted to large-scale preparation. Our mechanistic data suggest that the attack of RSK on S,S,S-trialkyl phosphorotrithioates and subsequent C-S bond cleavage, the Michaelis-Arbuzov-like dealkylation, are the key steps in the formation of (R1S)2P(S)OK.

Triethyl phosphorotrithioite reacts with linear and cyclic α-mono- and α,α-dihaloaldehydes by the Perkow reaction scheme to form O-vinyl phosphorotrithioates. It was established that catalytic amounts of zinc chloride much accelerate the reaction. 2005 Pl

The 34S isotope effect on the chemical shift of PIII nuclei in P(SR)3 esters is close to 20.6 ppb per PIII-34S bond, i.e. 3-4 times larger than for thiolo sulphur atoms in S=P(SR)3.A similar behaviour is noted for the P(-S-)3 sites in P4S9 and P4S3 and for the downfield triplet of P4S8, which, accordingly, is assigned to the tri-coordinate P atoms of this sulphide. 13C isotope effects are also reported for trialkyl(aryl) phosphorotrithioites and S,S,S-phosphorotrithioates.

Dialkyl trimethylsilyl dithiophosphites react with sulfenamides either through involvement of the trimethylsilyl group and the formation of trialkyl trithiophosphates or by isomerization of the starting silylphosphites to give S-alky O-trimethylsilyl alkyldithiophosphonates.The direction of the reaction depends on the nature of the substituents at the sulfur atoms of the silylphosphite and sulfenamide.

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